Pump tub assembly for redox flow battery

ABSTRACT

A redox flow battery includes an anolyte storage tank having a height configured for containing a quantity of an anolyte; a catholyte storage tank having a height configured for containing a quantity of a catholyte; an electrochemical cell configured for fluid communication with the anolyte and catholyte storage tanks; and a tub defining a cavity formed in at least one of the anolyte and catholyte storage tanks to provide a sealed fluid connection point below the height of the at least one storage tank.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.62/021,650, filed Jul. 7, 2014, the disclosure of which is expresslyincorporated by reference herein in its entirety.

BACKGROUND

Concerns over the environmental consequences of burning fossil fuelshave led to an increasing use of renewable energy generated from sourcessuch as solar and wind. The intermittent and varied nature of suchrenewable energy sources, however, has made it difficult to fullyintegrate these energy sources into existing electrical power grids anddistribution networks. A solution to this problem has been to employlarge-scale electrical energy storage (EES) systems. These systems arewidely considered to be an effective approach to improve thereliability, power quality, and economy of renewable energy derived fromsolar or wind sources.

In addition to facilitating the integration of renewable wind and solarenergy, large scale EES systems also may have the potential to provideadditional value to electrical grid management, for example: resourceand market services at the bulk power system level, such as frequencyregulation, spinning reserves, fast ramping capacity, black startcapacity, and alternatives for fossil fuel peaking systems; transmissionand delivery support by increasing capability of existing assets anddeferring grid upgrade investments; micro-grid support; and peak shavingand power shifting.

Among the most promising large-scale EES technologies are redox flowbatteries (RFBs). RFBs are special electrochemical systems that canrepeatedly store and convert megawatt-hours (MWhs) of electrical energyto chemical energy and chemical energy back to electrical energy whenneeded. RFBs are well-suited for energy storage because of their abilityto tolerate fluctuating power supplies, bear repetitive charge/dischargecycles at maximum rates, initiate charge/discharge cycling at any stateof charge, design energy storage capacity and power for a given systemindependently, deliver long cycle life, and operate safely without firehazards inherent in some other designs.

In simplified terms, an RFB electrochemical cell is a device capable ofeither deriving electrical energy from chemical reactions, orfacilitating chemical reactions through the introduction of electricalenergy. In general, an electrochemical cell includes two half-cells,each having an electrolyte. The two half-cells may use the sameelectrolyte, or they may use different electrolytes. With theintroduction of electrical energy, species from one half-cell loseelectrons (oxidation) to their electrode while species from the otherhalf-cell gain electrons (reduction) from their electrode.

Multiple RFB electrochemical cells electrically connected together inseries within a common housing are generally referred to as anelectrochemical “stack”. Multiple stacks electrically connected togetherare generally referred to as a “string”. Multiple stings electricallyconnected together are generally referred to as a “site”.

A common RFB electrochemical cell configuration includes two opposingelectrodes separated by an ion exchange membrane or other separator, andtwo circulating electrolyte solutions, referred to as the “anolyte” and“catholyte”. The energy conversion between electrical energy andchemical potential occurs instantly at the electrodes when the liquidelectrolyte begins to flow through the cells.

To meet industrial demands for efficient, flexible, rugged, compact, andreliable large-scale ESS systems with rapid, scalable, and low-costdeployment, there is a need for improved RFB systems.

SUMMARY

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the DetailedDescription. This summary is not intended to identify key features ofthe claimed subject matter, nor is it intended to be used as an aid indetermining the scope of the claimed subject matter.

In accordance with one embodiment of the present disclosure, a redoxflow battery is provided. The battery includes an anolyte storage tankhaving a height configured for containing a quantity of an anolyte; acatholyte storage tank having a height configured for containing aquantity of a catholyte; an electrochemical cell configured for fluidcommunication with the anolyte and catholyte storage tanks; and a tubdefining a cavity formed in at least one of the anolyte and catholytestorage tanks to provide a sealed fluid connection point below theheight of the at least one storage tank.

In accordance with any of the embodiments described herein, the tub maybe located such that a lower portion of the cavity is located below theliquid level in the tank and an upper portion of the cavity is locatedat or above the liquid level in the tank.

In any of the embodiments described herein, the tub may be a discreettub attached to the at least one storage tank.

In any of the embodiments described herein, the tub may be a tubassembly including a plurality of components that are sealably attachedto each other and to the at least one storage tank.

In any of the embodiments described herein, the cavity opening may belocated on the top wall of the at least one storage tank.

In any of the embodiments described herein, the cavity opening may belocated on the side wall of the at least one storage tank.

In any of the embodiments described herein, a fluid connection point mayinclude at least one of a pipe, pipe fitting, tube, tube fitting, pump,and filter, configured to transfer fluid between the storage tank andanother device or system that is external to the storage tank envelope.

In any of the embodiments described herein, a fluid connection point mayinclude at least one of a pipe, pipe fitting, tube, tube fitting, pump,and filter configured to transfer gas between the storage tank andanother device or system that is external to the storage tank envelope.

In any of the embodiments described herein, the cavity may contain aleak sensor configured to provide notification if liquid enters thecavity.

DESCRIPTION OF THE DRAWINGS

The foregoing aspects and many of the attendant advantages of thisdisclosure will become more readily appreciated by reference to thefollowing detailed description, when taken in conjunction with theaccompanying drawings, wherein:

FIG. 1 is an isometric view of a redox flow battery (RFB) module inaccordance with one embodiment of the present disclosure;

FIG. 2 is an isometric view of the RFB module of FIG. 1 with the outercontainer removed;

FIGS. 3A and 3B are schematic views of various components of the RFBmodule of FIGS. 1 and 2;

FIG. 4 is schematic view of a 1 MW site in accordance with oneembodiment of the present disclosure;

FIG. 5 is a schematic view of a 10 MW site in accordance with oneembodiment of the present disclosure;

FIG. 6 is a control diagram for a site, for example, the sites of FIG. 4or 5;

FIG. 7 is a close-up isometric view of pump tub assemblies shown in theRFB module of FIGS. 1 and 2 positioned on the top walls of therespective anolyte and catholyte tanks;

FIG. 8 is an exploded view of one pump tub assembly of FIG. 7;

FIG. 9 is a top view of one pump tub assembly of FIG. 7;

FIG. 10 is a side view of one pump tub assembly of FIG. 7;

FIG. 11 is a cross-sectional side view of a tank showing a pump tubassembly inserted into the tank;

FIGS. 12 and 13 are isometric views of an electrolyte transfer conduitshown in the RFB module of FIGS. 1 and 2;

FIGS. 14A, 14B, and 14C are schematic views of RFB modules havingnon-uniform anolyte and catholyte tank volumes in accordance withembodiments of the present disclosure;

FIGS. 15-21 are graphical depictions of data regarding electrolytestability and capacity management in an exemplary vanadium RFB system;

FIGS. 22-24 are graphical depictions of data regarding capacitymanagement in an exemplary vanadium RFB string;

FIGS. 25 and 26A-D are schematic drawings of various components of a gasmanagement system in accordance with embodiments of the presentdisclosure; and

FIGS. 27-30 are graphical depictions of data regarding gas management inan exemplary vanadium RFB module; and

FIG. 31 is a graphical depiction regarding energy density and averageoxidation state in an RFB module in accordance with one embodiment ofthe present disclosure; and

FIGS. 32 and 33 are isometric view of pump tub assemblies in accordancewith other embodiments of the present disclosure; and

FIG. 34 is an isometric view of an anti-siphon device in accordance withone embodiment of the present disclosure.

DETAILED DESCRIPTION

Embodiments of the present disclosure are directed to redox flowbatteries (RFBs), systems and components thereof, stacks, strings, andsites, as well as methods of operating the same. Referring to FIGS. 1-3,a redox flow battery 20 in accordance with one embodiment of the presentdisclosure is provided. Multiple redox flow batteries may be configuredin a “string” of batteries, and multiple strings may be configured intoa “site” of batteries. Referring to FIG. 4, a non-limiting example of asite is provided, which includes two strings 10, each having four RFBs20. Referring to FIG. 5, another non-limiting example of a site isprovided, which includes twenty strings 10, each having four RFBs 20.RFBs, systems and components thereof, stacks, strings, and sites aredescribed in greater detail below.

Redox Flow Battery

Referring to FIGS. 1 and 2, major components in an RFB 20 include theanolyte and catholyte tank assemblies 22 and 24, the stacks ofelectrochemical cells 30, 32, and 34, a system for circulatingelectrolyte 40, an optional gas management system 94, and a container 50to house all of the components and provide secondary liquid containment.

In the present disclosure, flow electrochemical energy systems aregenerally described in the context of an exemplary vanadium redox flowbattery (VRB), wherein a V³⁺/V²⁺ sulfate solution serves as the negativeelectrolyte (“anolyte”) and a V⁵⁺/V⁴⁺ sulfate solution serves as thepositive electrolyte (“catholyte”). However, other redox chemistries arecontemplated and within the scope of the present disclosure, including,as non-limiting examples, V²⁺/V³⁺ vs. Br⁻/ClBr₂, Br₂/Br⁻ vs. S/S²⁻,Br⁻/Br₂ vs. Zn²⁺/Zn, Ce⁴⁺/Ce³⁺ vs. V²⁺/V³⁺, Fe³⁺/Fe²⁺ vs. Br₂/Br⁻,Mn²⁺/Mn³⁺ vs. Br₂/Br⁻, Fe³⁺/Fe²⁺ vs. Ti²⁺/Ti⁴⁺, etc.

As a non-limiting example, in a vanadium flow redox battery (VRB) priorto charging, the initial anolyte solution and catholyte solution eachinclude identical concentrations of V³⁺ and V⁴⁺. Upon charge, thevanadium ions in the anolyte solution are reduced to V²⁺/V³⁺ while thevanadium ions in the catholyte solution are oxidized to V⁴⁺/V⁵⁺.

Referring to the schematic in FIG. 3A, general operation of the redoxflow battery system 20 of FIGS. 1 and 2 will be described. The redoxflow battery system 20 operates by circulating the anolyte and thecatholyte from their respective tanks that are part of the tankassemblies 22 and 24 into the electrochemical cells, e.g., 30 and 32.(Although only two electrochemical cells are needed to form a stack ofcells, additional electrochemical cells in the illustrated embodiment ofFIG. 3A include electrochemical cells 31, 33 and 35.) The cells 30 and32 operate to discharge or store energy as directed by power and controlelements in electrical communication with the electrochemical cells 30and 32.

In one mode (sometimes referred to as the “charging” mode), power andcontrol elements connected to a power source operate to store electricalenergy as chemical potential in the catholyte and anolyte. The powersource can be any power source known to generate electrical power,including renewable power sources, such as wind, solar, andhydroelectric. Traditional power sources, such as combustion, can alsobe used.

In a second (“discharge”) mode of operation, the redox flow batterysystem 20 is operated to transform chemical potential stored in thecatholyte and anolyte into electrical energy that is then discharged ondemand by power and control elements that supply an electrical load.

Each electrochemical cell 30 in the system 20 includes a positiveelectrode, a negative electrode, at least one catholyte channel, atleast one anolyte channel, and an ion transfer membrane separating thecatholyte channel and the anolyte channel. The ion transfer membraneseparates the electrochemical cell into a positive side and a negativeside. Selected ions (e.g., H+) are allowed to transport across an iontransfer membrane as part of the electrochemical charge and dischargeprocess. The positive and negative electrodes are configured to causeelectrons to flow along an axis normal to the ion transfer membraneduring electrochemical cell charge and discharge (see, e.g., line e⁻ inFIG. 3A). As can be seen in FIG. 3A, fluid inlets 48 and 44 and outlets46 and 42 are configured to allow integration of the electrochemicalcells 30 and 32 into the redox flow battery system 20.

To obtain high voltage, high power systems, a plurality of singleelectrochemical cells may be assembled together in series to form astack of electrochemical cells (referred to herein as a “stack,” a “cellstack,” or an “electrochemical cell stack”), e.g., 30 or 32 in FIG. 3A.Several cell stacks may then be further assembled together to form abattery system 20. A MW-level RFB system generally has a plurality ofcell stacks, for example, with each cell stack having more than twentyelectrochemical cells. As described for individual electrochemicalcells, the stack is also arranged with positive and negative currentcollectors that cause electrons to flow through the cell stack generallyalong an axis normal to the ion transfer membranes and currentcollectors during electrochemical charge and discharge (see, e.g., line52 shown in FIG. 3A).

The ion exchange membrane in each electrochemical cell preventscrossover of the active materials between the positive and negativeelectrolytes while supporting ion transport to complete the circuit. Ionexchange membrane material, in a non-limiting example, a perfluorinatedmembrane such as NAFION or GORE-SELECT, may be used in theelectrochemical cells.

Ion exchange through the membrane ideally prevents the transport ofactive materials between the anolyte and catholyte. However, dataobtained from operating vanadium redox batteries (VRBs) shows capacityfading over time when the system is operating without any capacityfading mitigation features as described herein. Such capacity fadingmay, at least in part, be attributed to some transport of vanadium ionsacross the membrane. Different vanadium cations in the system havedifferent concentration diffusion coefficients and electric-migrationcoefficients for crossing over through the membrane. These differencescontribute to an unbalanced vanadium transfer between anolyte andcatholyte after multiple cycles of operation, which may result in a lossof energy storage capacity.

Other negative effects caused by the transport of vanadium ions acrossthe membrane include precipitation, which may occur if the vanadium ionconcentration in the catholyte continues to increase as a result of thenet transfer of vanadium ions. Precipitate may form in the electrodestacks, which may result in degradation in the performance of the VRBsystem. As a non-limiting example, precipitation of V⁵⁺ as V₂O₅ canoccur in the catholyte (thereby decreasing the amount and/or theconcentration and amount of V⁵⁺ in the catholyte).

In addition to the transport of vanadium ions across the membrane andprecipitation, other electrochemical side reactions may contribute todecreased performance in VRB systems. These reactions must also beaddressed to maximize the capacity and service life of the system, whileminimizing cost and service requirements for the life of the battery.For example, under some operating conditions, side reactions may produceexcess hydrogen and chlorine gases in the headspaces of the anolyteand/or catholyte tanks. Other detrimental reactions may also occur whenelectrolyte is exposed to oxidizing agents such as oxygen. In oneexample, over time, the anolyte is susceptible to V²⁺ oxidation byatmospheric oxygen that is introduced into the tank during maintenance,installation, or other operations (thereby decreasing the amount and/orconcentration of V²⁺). V²⁺ can also be oxidized by H⁺ if hydrogen isevolved at the anode (thereby decreasing the amount and/or concentrationof V²⁺ in the anolyte).

Described herein are systems and methods of operation designed formitigating the capacity decaying effects described above to improve RFBperformance on a battery, string, and site level. In general, thesefeatures can be described in terms of maintaining electrolyte stabilityby applying active and passive charge balancing, employing specificmethods for analysis and adjustment of electrolyte composition, andprocess gas management.

String and Site Control System

As noted above, a string 10 is a building block for a multiple MW site.As seen in the exemplary layouts in FIGS. 4 and 5, each string 10includes four battery containers connected in series to a power andcontrol system (PCS) 12 container. As can be seen in FIG. 6, the controlsystem for each string includes a battery management system (BMS) 14with local control provided by a human machine interface (HMI) 16. TheBMS 14 interprets remote commands from the site controller 18, forexample, a customer requirement to charge or discharge, as itsimultaneously directs the appropriate operations for each battery andsub-component in the string 10 via a communication network. At the sametime, according to programmed logic, the BMS 14 interprets string 10operating data from the batteries 20, PCS, and their associatedsub-components to evaluate service or diagnose maintenance requirements.See also FIG. 6 for string and site control diagrams.

As a non-limiting example, an exemplary VRB may have capacity up to 125kW for four hours (500 kW-hours) and a storage string may have capacityup to 500 kW for four hours (2 MW-hours). To be effective as a largescale energy storage system that can be operated to provide multiplelayered value streams, individual batteries, designed and manufacturedto meet economies of scale, may be assembled as building blocks to formmultiple-megawatt sites, for example 5 MW, 10 MW, 20 MW, 50 MW, or more.Managing these large installations requires multi-level control systems,performance monitoring, and implementation of various communicationsprotocols.

Referring to FIG. 4, an exemplary 1 MW system layout shows two 500 kWbuilding block sub-assemblies or strings 10 that each include fourbattery modules 20 and one PCS module 102. Using this approach,multi-level larger systems may be assembled, for example, thesingle-level 10 MW system shown in FIG. 5. As described in greaterdetail below, the unique combination of systems and components describedherein provide significantly more energy density in a compact flowingelectrolyte battery module 20 and string 10 design than previouslydesigned flowing electrolyte batteries, such earlier generation VRBs.Other hybrid flowing electrolyte batteries, such as ZnBr2 systems, maydemonstrate similar characteristics.

Battery Container System, Electrolyte Tank Assembly, and GeneralArrangement

Referring now to FIGS. 1 and 2, each RFB 20 includes a container 50 thathouses the remaining components of the system in a substantially closedmanner. These remaining components generally include the anolyte andcatholyte tank assemblies 22 and 24, the stacks of electrochemical cells30, 32, and 34, a system for circulating electrolyte 40, and an optionala gas management system 94. The configuration of each of thesecomponents will now be described in more detail.

FIG. 1 depicts the container 50 that houses, for example, the componentsshown in FIG. 2. The container 50 can be configured in some embodimentsto be an integrated structure that facilitates or provides one or moreof the following characteristics: compact design, ease of assembly,transportability, compact multiple-container arrangements andstructures, accessibility for maintenance, and secondary containment.

In the illustrated embodiment of FIGS. 1 and 2, the representativecontainer 50 comprises two major compartments that house components ofthe RFB 20. In some embodiments, the division between the first andsecond compartments 60 and 62 is a physical barrier in the form of abulkhead 70 (see FIG. 3B), which may be a structural or non-structuraldivider. The bulkhead 70 in some embodiments can be configured toprovide secondary containment of the electrolyte stored in tankassemblies 22 and 24. In another embodiment, a secondary structural ornon-structural division can be employed to provide a physical barrierbetween the anolyte tank 22 and the catholyte tank 24. In either case,as will be described in more detail below, the tanks 22 and 24 areconfigured as so to be closely fitted within the compartment orcompartments, thereby maximizing the storage volume of electrolytewithin the container 50, which is directly proportional to the energystorage of the battery 20.

In some embodiments, the container 50 has a standard dimensioning of a20 foot ISO shipping container. In one representative embodiment shownin FIGS. 1 and 2, the container has a length A which may be 20 feet, 8feet in width B, and 9½ feet in height C, sometimes referred to as aHigh-Cube ISO shipping container. Other embodiments may employ ISOdimensioned shipping containers having either 8 feet or 8½ feet inheight C, and in some embodiments, up to 53 feet in length A. In some ofthese embodiments, the container 50 can be additionally configured tomeet ISO shipping container certification standards for registration andease of transportation via rail, cargo ship, or other possible shippingchannels. In other embodiments, the container may be similarlyconfigured like an ISO shipping container. In other embodiments, thecontainer has a length in the range of 10-53 feet and a height in therange of 7-10 feet.

The container 50 also includes various features to allow for the RFB 20to be easily placed in service and maintained on site. For example,pass-through fittings are provided for passage of electrical cablingthat transfers the power generated from circulation of the anolyte andthe catholyte through the stacks of electrochemical cells. In someembodiments, the container 50 includes an access hatch 80, as shown inFIG. 1. Other hatches, doors, etc. (not shown) may be included forproviding access to systems of the RFB 20.

Electrolyte Tank and Assembly

FIGS. 1 and 2 illustrate anolyte tank 22 and catholyte tank 24positioned side by side in the second compartment 62. In the illustratedembodiment shown in FIGS. 1 and 2, the representative anolyte tank 22 isgenerally rectangular, with a shoulder or stepped section 90 located atthe front upper corner of each tank 22 and 24.

The stepped section 90 provides access for an optional electrolytetransfer conduit 92 to provide fluid communication between the anolytetank 22 and the catholyte tank 24 when the tanks are alignedside-by-side, as described in greater detail below. However, inaccordance with other embodiments of the present disclosure, the tanks22 and 24 need not be manufactured to include a stepped section 90 ormay include another configuration to optionally accommodate either anelectrolyte transfer conduit or another fluid transfer device betweentanks 22 and 24.

In some embodiments, anolyte tank 22 and/or catholyte tank 24 areconstructed from molded or fabricated plastic, fiberglass, or othermaterials or combinations of materials. Other materials may includevarious metals, glass, glass lined steel, tantalum, etc. In someembodiments, tanks 22 and/or 24 have a rigid construction. In someembodiments, the material comprising the walls of the tanks 22 and/or 24are configured to flex outwardly when filled with electrolyte in orderto contain the electrolyte therein. As such, the tanks in someembodiments can expand or contract to accommodate the expected range ofchanges in electrolyte volume or pressure during operation.

In some embodiments, anolyte tank 22 and/or catholyte tank 24 areconstructed such that some portions of the tanks are more rigid tosupport equipment or other features attached to the tanks, while otherportions of the tanks may retain flexibility as described above.

The catholyte tank 24 is configured substantially similar to the anolytetank 22. In one embodiment of the present disclosure, the catholyte tank24 has a smaller volume than the anolyte tank 22, as described ingreater detail below. An optimized tank size ratio between the anolyteand catholyte tanks 22 and 24 provides a means to maintain maximumenergy storage capacity of the RFB module 20 over multiple cycles. Thedifference in volume between the anolyte and catholyte tanks 22 and 24can be realized via a larger width dimension, for example, of theanolyte tank 22, or the tanks can have identical outer dimensions butthe catholyte tank 24 may include a cavity bottom that is higher thanthe floor of the tank or a filler material, such as an inert material,that takes up some of the volume of the tank. In other embodiments (notshown), the anolyte tank may have substantially the same volume as thecatholyte tank or may have a smaller volume than the catholyte tank.

In some embodiments, the anolyte tank 22 and the catholyte tank 24 areconfigured so as to store a combined volume of electrolyte of about 20cubic meters or greater. In one representative embodiment, the totalcombined volume is about 23 cubic meters or greater.

As shown in FIG. 2, the tanks 22 and 24 are sized to fit closely intothe container 50. For example, the length of each tank 22 and 24 is suchthat they abut against a front bulkhead 70 at one end (see FIG. 4) andagainst a container back wall 72 at their opposite end (see FIGS. 1 and4). Therefore, the back wall 72 of the container 50 supports the back ofthe tanks 22 and 24, and the front bulkhead 70 installed, for example,after tank installation supports the front of the tanks 22 and 24.Similarly, the height of each tank 22 and 24 is that that the tanks aresupported by the side walls 74, extending from the bottom wall 76 of thecontainer 50 and extend upwardly to just proximal the top wall 78 (seeFIG. 1).

In one embodiment of the present disclosure, the anolyte tank and thecatholyte tank are configured to extend between the bulkhead and a firstend wall that define the first compartment so as to be adjacent or abutagainst the bulkhead and the end wall. In another embodiment, the areadefined by lengthwise sidewalls and widthwise side walls of the anolytetank and the catholyte tank fills at least 85% of the area defined bythe anolyte and catholyte tank compartments.

To increase rigidity and strength of the container 50, and to withstandadditional side loading imparted by the electrolyte in the tanks 22 and24, the vertically disposed side wall walls 74 can be reinforced. Otherwalls may also be reinforced or constructed with increased strength. Forexample, the back wall 72 can also be reinforced and the bottom wall 76can be constructed with thicker steel or multiple steel plates in orderto support the weight of the electrolyte. It will be appreciated thatthe bulkhead 70 also provides for increased rigidity of the container.In one embodiment, the container 50 has a unibody construction. Thestructural support provided by the container 50 when the tanks 20 and 24are filled with electrolyte allows for the tanks 22 and 24 to bemanufactured similarly to bladders that have minimal inherentself-supporting structure

To reduce the possibility of an electrolyte leak from the tanks 22 and24, penetrations into the tanks 22 and 24 below the level of the liquidstored are minimized. In the illustrated embodiment, there is onepenetration into each tank 22 and 24 slightly below the liquid level toaccommodate electrolyte transfer conduit 92. As described in greaterdetail below, the electrolyte transfer conduit 92 is positioned near thetop of each tank 22 and 24, and there is a well 172 to control any leakthat may occur at the joints between the conduit 92 and the tanks 22 and24 (see FIG. 13).

In the event of a leak of electrolyte in the RFB module 20, thecontainer 50 is manufactured to provide secondary electrolytecontainment. In that regard, the container may be manufactured fromsteel or another suitable metal or another suitable material, and allseams are fully welded or sealed to provide secondary leak containment.

Pump Tub (Electrolyte Tank Sub-Assembly)

To maximize the size and liquid fill level of the tanks 22 and 24, whilealso avoiding leak concerns due to penetrations below the liquid level,a low-profile pump tub assembly 120 can be employed in accordance withaspects of the present disclosure. When installed, as will be describedin more detail below, the pump tub assembly 120 provides electrolytesuction and discharge access below the tank liquid level, while keepingliquid connections physically located above the tank liquid level. Thepump tub assembly 120 can also be equipped with leak sensors (notshown). The tub is located such that a lower portion of the cavity islocated below the liquid level in the tank and an upper portion of thecavity is located at or above the liquid level in the tank.

Referring to FIGS. 1 and 2, the pump tub assembly 120 is disposed at theforward section of the top wall 78 of each tank 22 and 24. Referring nowto FIGS. 7-11, the pump tub assembly 120 will be described in greaterdetail. As can be seen in the illustrated embodiment of FIG. 8, the pumptub assembly 120 includes a tub 124 that is generally cylindrical,although other shapes may be utilized. The tub 124 includes acontiguous, cylindrical sidewall 126 that extends from a bottom wall 128upwardly to an upper edge, thereby delimiting an open-ended cavity 130.The cavity 130 is configured to house various piping connectionsinterfaces and optional filters, etc. In the illustrated embodiment, thetub assembly also houses a pump and a filter. In other embodiments, thepump, filter, or other components may be located in another location inthe system, for example, in the first compartment 60.

At the opening to the cavity 130, the tub 124 includes a laterallyoutwardly extending flange 138 that extends the entire perimeter of thetub sidewall 126. When assembled, the tub 124 is inserted into acooperatingly configured opening 140 in the top wall 142 of each tank 22or 24 and placed such that the flange 138 abuts the top wall 142. Oncemounted as part of the tank container system described above, the pumptub provides a high electrolyte fill level, low equipment profile, notank penetrations for electrolyte circulation below the liquid level andin some embodiments moves the pumps, filters, and associated equipmentout of the space in front of the tanks to make it available for balanceof plant (BOP) components that comprise electrical systems, stacks,electrolyte manifold distribution systems, and air handling systems.Compared to existing VRB systems, maximized electrolyte tank volume andBOP space provided by the tank/pump/container system result in anincrease in energy density in the battery unit 20.

It will be appreciated that an O-ring or other type of sealing device136 can be disposed between the flange 138 of the tub 124 and the topwall 142, if desired (see FIG. 11). Any suitable fastening technique canbe employed to couple the tub to the tanks 22 and 24 in a substantiallysealed and leak proof manner.

Now referring to FIGS. 32 and 33, pump tub assemblies in accordance withother embodiments of the present disclosure will be described in moredetail. The pump tub assemblies 220 and 320 of FIGS. 32 and 33 aresubstantially identical in materials and operation as the previouslydescribed embodiment, except for differences regarding the location ofthe pump tub relative to the housing, which will be described in greaterdetail below. For clarity in the ensuing descriptions, numeralreferences of like elements of the pump tub assembly 120 are similar,but are in the 200 and 300 series for the respective illustratedembodiments of FIGS. 32 and 33.

Referring to FIG. 32, the pump tub assembly 220 includes a tub sidewall226 that intersects with the top tank wall 278 and one or more tank sidewalls 270. Such configuration allows for front access to the pump tubassembly 220, as compared to only top access in the previously describedembodiment (see FIG. 1).

The tub is located such that a lower portion of the cavity is locatedbelow the liquid level in the tank and an upper portion of the cavity islocated at or above the liquid level in the tank. The tub may be adiscreet tub attached to a tank, or may include a plurality ofcomponents that are sealably attached to each other and to the tank.

Referring to FIG. 33, the pump tub assembly 320 includes a tub sidewall326 that, like the pump tub assembly 320 of FIG. 32, also intersectswith the top tank wall 378 and one or more tank side walls 370. However,the pump tub assembly 320 is semi-circular in cross-section and thefront portion 326 of the pump tub assembly 320 is flush with the frontwall 370 of the tank 322. In this design, the front portion 326 of thepump tub assembly 320 does not extend beyond the front wall 370 of thetank 322. Like the pump tub assembly 220 of FIG. 32, such configurationallows for front access to the pump tub assembly 320.

In both of the illustrated embodiments of FIGS. 32 and 33, the sides andtop of the pump tub assemblies 220 and 320 can be sealed to the tank bywelding, with gaskets, or other common sealing techniques. Also, in bothembodiments, all or part of the pump tub assemblies 220 and 320 shown inFIGS. 32 and 33 may be molded into the tanks. In either embodiment, anyportions of the molded tub that are below the tank liquid level can beprovided with leak containment by installing an additional sealing bodythat can be sealed to the tank by welding, with gaskets, or other commonsealing techniques.

In one embodiment of the present disclosure, a fluid connection pointincludes at least one of a pipe, pipe fitting, tube, tube fitting, pump,and filter, configured to conduct fluid between the storage tank andanother device or system that is external to the storage tank envelope.

In another embodiment, a fluid connection point includes at least one ofa pipe, pipe fitting, tube, tube fitting, pump, and filter configured toconduct gas between the storage tank and another device or system thatis external to the storage tank envelope.

Electrolyte Circulation System

As described above regarding the general operation of a RFB 20, anelectrolyte circulating system 40 is provided for circulating theanolyte and the catholyte from respective tanks 22 and 24 into thestacks of electrochemical cells 30, 32, and 34 (see FIG. 2). In thatregard, discharge and return conduits/piping for each tank 22 and 24 aresuitably connected from/to the stacks of electrochemical cells 30, 32,and 34, as shown in FIGS. 2, 3 and 7. In some embodiments, a shuntcurrent suppression system may be employed by the circulation system 40for the anolyte circuit and/or the catholyte circuit, as set forth inco-pending U.S. patent application Ser. No. 14/217,077, filed Mar. 17,2014, the disclosure of which is incorporated by reference herein in itsentirety. In the illustrated embodiment, the shunt current suppressionsystem includes looping or coiled tubing 88 to maximize the travel pathof the electrolyte (and effectively minimize shunt currents) whilekeeping pumping losses to a minimum in a compact space.

As shown in FIGS. 2, 9 and 10, each pump tub assembly 120 includes apiping interface 144 for coupling the tanks 22 and 24 in fluidcommunication with the return and discharge piping of the circulatingsystem 40. For example, in the embodiment shown (see FIG. 9), the pipinginterface 144 includes a discharge connector 148 in the form of aflanged pipe connected to the interior of the tank via a motor drivenpump 152 and a suction tube 156 that extends downward into theelectrolyte (see FIG. 10). The piping interface 144 also includes areturn connector 160 in the form of a flanged pipe connected to theinterior of the tank (see FIG. 9) via an elongated down tube 164 (seeFIG. 10). In the embodiment shown, an optional filter 158 can besuitably interconnected between the discharge connector 148 and the pump152 (see FIG. 10).

The piping interface 144 may also include a third connector 170 in thepump tub assembly 120 for providing the gas pressure management system96 access to the head space 178, as will be described in greater detailbelow. Other interfaces may also be provided, including a fill connector172 adapted to be connected to a fill tube 166 positioned in therespective tank. It will be appreciated that all penetrations throughthe bottom or side wall of the tub are both substantially sealed andabove the tank liquid level.

As described in greater detail below with reference to FIGS. 12-14, theRFB module 20 may further include an optional electrolyte transferconduit 92 allowing fluid exchange between the catholyte and anolytetanks 24 and 22 and an optional gas management system 94 for managingevolving gases from the catholyte and anolyte and gas pressure in theheadspaces during operation (see FIG. 13). Both of these elements arepart of systems that can be used to maintain the energy density andcapacity of the RFB module 20, and reduce periodic maintenance.

Electrolyte Stability and Capacity Management

As described previously, during normal charge/discharge operationswithout corrective action, a decrease in charge capacity may beexperienced in VRB systems. Exemplary test data was sampled during 110continuous charge/discharge cycles, and plotted as a function of thenumber of cycles on a representative 31.5 kW stack. The data in FIGS.15-19 illustrate the following: electrolyte volume change during cycling(FIG. 15); electrolyte total vanadium change during cycling (FIG. 16);electrolyte active available material change during cycling (FIG. 17);electrolyte concentration change during cycling (FIG. 18); andelectrolyte capacity fading during cycling (FIG. 19), each described ingreater detail below.

Example 1 Electrolyte Volume Change

Referring to FIG. 15, catholyte volume increased approximately 50 litersover 110 cycles, while at the same time the anolyte volume decreasedapproximately 50 liters over the same number of operating cycles. Volumeratio change continued to diverge at approximately the same rate duringthe course of testing. No stabilization was observed.

Example 2 Electrolyte Total Vanadium Change

Referring to FIG. 16, the number of moles of vanadium in the catholyteincreased from approximately 800 to 1010 over 110 cycles, while at thesame time, the number of moles of vanadium in the anolyte decreased fromapproximately 800 to 560 over the same number of operating cycles.Although the total vanadium rate of change decreased over time, it stillcontinued to diverge at the end of testing. No stabilization wasobserved.

Example 3 Electrolyte Active Available Material Change

Referring to FIG. 17, the number of moles of vanadium active materials(VO 2+) in the catholyte increased from approximately 700 to 900 over110 cycles, while at the same time, the number of moles of vanadiumactive materials (V 3+) in the anolyte decreased from approximately 700to 220 over the same number of operating cycles. The active availablematerial rate of change in the catholyte tank decreased over time, butstill continued to diverge at the end of testing. The active availablematerial rate of change in the anolyte tank continued to decrease at ahigh rate at the end of testing, and was the limiting factor indetermining the energy storage capacity of the battery. No stabilizationwas observed.

Example 4 Electrolyte Concentration Change

Referring to FIG. 18, the molar concentration of the positiveelectrolyte (catholyte) increased from approximately 2.1M to 2.3M overthe first 20 cycles, and then stabilized at approximately thatconcentration for the remaining cycles. At the same time, the negativeelectrolyte (anolyte) decreased from approximately 2.1M to 1.8M over thefirst 20 cycles, and then stabilized at approximately that concentrationfor the remaining cycles. This demonstrated relationship illustrates aninherent VRB characteristic that provides insight into preferred volumeratios between the anolyte and catholyte tanks. In this example, theratio is approximately 1.25:1.

Example 5 Electrolyte Capacity Fading

Referring to FIG. 19, the total energy capacity of the electrolyte inWatt-hours/liter, without any mitigating designs or procedures in place,shows a decrease for an initial value of 18 to a value of 4.5 after 110cycles, reflecting information shown in the previous plots.

Electrolyte Adjustments for Managing Energy Storage Capacity

As described previously, and as can be seen in FIG. 18, the relationshipbetween electrolyte concentration in the anolyte and catholyte tanksgenerally remains constant after the initial start-up phase; however atthe same time, as can be seen in FIGS. 15 and 17, due to the inherentchemical reactions, nature of the cell structure, and other factors, thevolume and active materials in the anolyte and catholyte tanks change ascycle numbers increase. As described previously, and as can be seen inFIG. 19, without mitigation, the battery energy capacity degrades overtime as the result of limited availability of active material in theanolyte tank. Therefore, a system that maintains a specific electrolyteconcentration ratio between the anolyte and catholyte tanks and/ormaximizes the available active materials for energy storage and dispatchis described herein.

Electrolyte Volume Ratio

In one embodiment of the present disclosure, a method of operating aredox flow battery includes having a uniform or non-uniformpredetermined volume ratio, based on maintaining a preferred electrolyteconcentration, between the quantity of anolyte and the quantity ofcatholyte in the system. In the case of non-uniform predetermined volumeratio, the quantity or volume of anolyte may be more or less than thequantity or volume of the catholyte. The predetermined starting volumeratio may be different from or the same as the predetermined volumeratio during operation. Moreover, the predetermined volume ratio duringoperation may change subject to other conditions in the system.

As non-limiting examples, the tank volume ratio may have an anolytevolume to catholyte volume ratio of about 1:1.05 to about 1:1.50, about1:1.15 to about 1:1.35, or about 1:1.20 to about 1:1.30. As anon-limiting example, in the illustrated embodiment of FIG. 2, the tankvolume ratio between the anolyte tank and the catholyte tank is about1.25:1.

As other non-limiting examples, the tank volume ratio may have acatholyte volume to anolyte volume ratio of about 1:1.05 to about1:1.50, about 1:1.15 to about 1:1.35, or about 1:1.20 to about 1:1.30.

A non-uniform tank volume ratio may be achieved by having two differenttank dimensions. For example, see the tank dimensions in the illustratedembodiment of FIG. 2. In that regard, the catholyte and anolyte tankshave similar heights and length dimensions, but different widthdimensions (see schematic view in FIG. 14A). In another embodiment, thetanks may have different depths. For example, see the tank dimensions inthe alternate embodiment of FIG. 14B. In that regard, the catholyte andanolyte tanks 224 and 222 have similar height, width, and lengthdimensions, but different depths dimensions. In other embodiments, thetanks may be partially filled with non-reacting materials to reduce someof the tank volume, or the tank may have a changeable volume to accountfor changes in the operation of the system (see alternate embodiment ofFIG. 14C).

As described above, a non-uniform tank volume ratio based on maintaininga preferred electrolyte concentration between the anolyte and catholytetanks can improve the energy density achieved during operation of theRFB module 20 having a given capacity for holding a certain amount ofelectrolyte. As a non-limiting example, a tank volume ratio of about1.25:1 between the anolyte tank and the catholyte tank in theillustrated embodiment of FIG. 2 achieves greater energy density for thesame total amount of electrolyte as compared to a uniform tank volumeratio between the anolyte and catholyte tanks. In addition, theinventors have found an advantageous effect of a non-uniform tank volumeratio that maintains a preferred electrolyte concentration, such as aratio of about 1.25:1 between the anolyte tank and the catholyte tank inthe illustrated embodiment of FIG. 2, maintains improved energy densityover time than tanks of uniform size. Greater energy density is a resultof greater availability and utilization of the active species in theelectrolyte. In other types of modules, for example, in non-vanadium RFBsystems, a preferable tank volume ratio may vary from the preferredrange for a VRB system, and for example, may have a greater volume ofcatholyte compared to anolyte.

Electrolyte Transfer

In accordance with one embodiment of the present disclosure, the RFB 20has a predetermined volume ratio, based on maintaining a preferredelectrolyte concentration, in accordance with the volume ratios ofcatholyte and anolyte, as described above. Over a period of time ofnormal operation of the redox flow battery, the volume ratio of theanolyte and the catholyte may become greater than or less than thepredetermined volume ratio. For example, as can be seen in the exemplarydata of FIG. 15, in one mode of operation, a VRB system gains catholytevolume and loses anolyte volume over long-term cycling.

Therefore, in accordance with embodiments of the present disclosure, avolume of catholyte from the catholyte storage tank 24 to the anolytestorage tank 22, or a volume of anolyte from the anolyte storage tank 22to the catholyte storage tank 24, to restore the volume ratio to thepredetermined volume ratio. In the exemplary system of FIG. 15, excesscatholyte generated from the system would need to flow from thecatholyte tank 24 to the anolyte tank 22 to correct the volumeimbalance.

Such transfer may be affected by passive electrolyte transfer, activeelectrolyte transfer, or a combination of passive and active electrolytetransfer, all described in greater detail below.

Passive Transfer of Electrolyte

In one embodiment of the present disclosure, a passive mechanicalarrangement allows for the transfer of electrolyte between the anolyteand catholyte tanks. The transfer may be from anolyte tank 22 tocatholyte tank 24 or from catholyte tank 24 to anolyte tank 22.

In the illustrated embodiment of FIGS. 1 and 2, the passive transfersystem is a tank electrolyte transfer conduit 92. Referring to asimplified schematic in FIG. 14, and the RFB module 20 views in FIGS.11-13, the electrolyte transfer conduit 92 is located at an overflowlevel in either the catholyte or anolyte tank 22 or 24. As discussedabove, a stepped section 90 in each of the anolyte and catholyte tanks22 and 24 provides access for an optional electrolyte transfer conduit92 to provide fluid communication between the anolyte tank 22 and thecatholyte tank 24 when the tanks are aligned side-by-side.

In this configuration, flow rate of electrolyte between the tanks 22 and24 is determined based on the level differences. In the illustratedembodiment of FIGS. 12 and 13, the anolyte tank 22 is sized to have alarger volume than the catholyte tank by having a larger width dimension(see also schematic view in FIG. 14A). As described above, in alternateembodiments, the depth of the catholyte tank 224 or 324 may be reducedas compared to the anolyte tank 222 or 322 by increasing the thicknessof the bottom wall of the catholyte tank 224 (see FIG. 14B) or bypartially filling the catholyte tank 324 with non-reacting materials toreduce some of the tank volume (see FIG. 14C).

As described in EXAMPLE 1 above in a VRB system, without a transfer ofelectrolyte between the anolyte and catholyte tanks 22 and 24, catholytevolume increases over time, which affects the capacity of the systemover time. The electrolyte transfer conduit 92 located at the overflowlevel in the illustrated embodiment allows for the flow of catholytefrom the catholyte tank 24 as the catholyte volume increases into theanolyte tank 22 (see exemplary schematic in FIG. 14A).

In the illustrated embodiment, the electrolyte transfer conduit 92penetrates each tank 22 and 24 slightly below the liquid level toaccommodate electrolyte transfer conduit 92. To control any leak thatmay occur at the joints between the conduit 92 and the tanks 22 and 24,the conduit connections 168 with each tank 22 and 24 in the illustratedembodiment of FIGS. 12 and 13 are flanged connections 168 surrounded bya well 172 molded into the tanks 22 and 24 at the stepped section 90.The wells 172 may include leak sensors to detect any leaks that mayoccur. In addition, the conduit connections 168 may include other leakprevention devices, such as unions, axial O-ring fittings, etc.

In the illustrated embodiment, the electrolyte level in each of thetanks 22 and 24 may be set so as to allow for the transfer of onlyliquid electrolyte or of both liquid electrolyte and gas (from theheadspaces in the catholyte and anolyte tanks, see e.g., exemplarydiagram in FIG. 25) through the electrolyte transfer conduit 92. If atransfer of gas from the headspaces in the catholyte and anolyte tanksis provided, the electrolyte transfer conduit 92 is also a part of thegas management system 94 for the battery, as described in greater detailbelow.

In one embodiment of the present disclosure, the electrolyte transferconduit delivers excess catholyte to the anolyte tank 22 duringoperation to account for the volumetric increase in the catholyte andreturn the system to a predetermined volume ratio.

In accordance with other embodiments of the present disclosure, thetanks 22 and 24 need not be manufactured to include a stepped section 90or may include another configuration to accommodate either anelectrolyte transfer conduit or another fluid transfer device betweentanks 22 and 24. For example, a suitable electrolyte transfer conduitmay be located not at an overflow position, but instead below the liquidlevel in each of the tanks. In such a configuration, the electrolytetransfer conduit would provide continuous electrolyte exchange betweenthe anolyte and catholyte. The rate of exchange may be determined inpart by the length and diameter of the transfer conduit.

In addition to passive electrolyte transfer mechanisms, activeelectrolyte transfer mechanisms are also discussed below.

Example 6 Long-Term Performance of Auto-Balanced System

Exemplary test data was sampled during over 1000 continuouscharge/discharge cycles, and plotted as a function of the number ofcycles on a representative 31.5 kW stack. The test system included apassive overflow electrolyte transfer conduit in accordance withembodiments of the present disclosure. Test data in FIG. 20 shows theelectrolyte transfer conduit achieved substantially uniform catholyteand anolyte volumes, catholyte to anolyte vanadium concentration ratio,and catholyte to anolyte total vanadium ratio for more than 1000 fullcharge/discharge cycles. Test data in FIG. 21 shows substantiallyuniform Coulombic efficiency, voltage efficiency, energy efficiency, andenergy density for more than 1000 full charge/discharge cycles.

Active Transfer of Electrolyte

In addition to, or in lieu of the passive transfer system, the RFBmodule 20 may include an active transfer system configured for activelytransferring electrolyte from one to the other of the catholyte andanolyte tanks. Such active transfer may include pumping or otherwisecontrolling electrolyte tank-to-tank transfer using a valve system. Theactive transfer may be automatically controlled based on systemconditions or manually controlled by an operator.

If a combination of passive and active electrolyte transfer systems isemployed, the active system may use the same or a separate electrolytetransfer conduit as the passive system.

Electrolyte Capacity Adjustment Using Additives

In addition to electrolyte transfer between the anolyte and catholytetanks, electrolyte capacity can also be adjusted by adding reductivereagents to the positive electrolytes. Suitable reagents may includehydrocarbons, such as fructose. These reductive reagents can be oxidizedby the catholyte, releasing carbon dioxide. Such reductive reagents maybe added periodically, for example, during scheduled maintenance orautomatically by the BMS system during battery operation.

Fructose added to the catholyte is reduced according to the followingformula, consuming hydrogen and generating carbon dioxide and water:

C₆H₁₂O₆+24VO₂ ⁺+24H⁺=24VO²⁺+6CO₂↑+18H₂O.

String Capacity Management of Electrolyte

As described above, passive capacity management has been shown tomaintain stable performance under most conditions for a single battery.However, other operating conditions may occur that require activecapacity management, especially on the string and site level.

In one example, stack variation caused by differences in manufacturingassembly and materials may produce slightly different performancecharacteristics between each of the four RFBs 20 in a string 10 (seeexemplary string diagrams in FIGS. 2 and 6), in some cases leading todifferent membrane ion transfer capabilities or different levels of sidereactions, both of which contribute to performance mismatch in a stringof batteries. One mechanism that may be affected by manufacturingdifferences in stacks can be seen during battery operation in the wayions travel back and forth through the membrane separating positive andnegative electrolytes as they form a closed electrical circuit, and inthe way water molecules travel through the membrane together with otherhydrated ions or by themselves. As a result of stack differences, thevolume of the positive and negative electrolytes and the concentrationsof active ions in the electrolytes may change at different rates duringbattery operation.

In another example, stack variations caused by damage (leakage,blockage, etc.) to one or more stack cells may produce slightlydifferent performance characteristics when the stacks are assembled asbatteries and strings, and may also cause an imbalance in thepredetermined battery tank volume ratio described above. Other reasonsfor stack variation may include differences in the electrode, stackcompression, etc.

Because there may be performance differences between batteries in astring and all batteries in a string are electrically connected forcharge and discharge operations, the worst performing battery determinesthe performance of the string. Further, because each battery in thestring has dedicated electrolyte tanks, lower performing batteries maycontinue to experience declining performance caused, for example by theby stack variation described above. Declining battery capacity isgenerally indicative of or may lead to electrolyte stability andcapacity problems for the associated string. If left unchecked, theseperformance variations may result in decreased capacity across a site.

Exemplary test data showing string declining performance is illustratedbelow in EXAMPLES 7 and 8.

Example 7 Energy Density

In a string of three, series-connected, kW-scale batteries withoutcapacity management adjustments, a steady decline in energy density over35 cycles can be seen in FIG. 22.

Example 8 Open Circuit Voltage

In a string of three, series-connected, kW-scale batteries withoutcapacity management adjustments, a steady deviation in open circuitvoltage (OCV) at the end of discharge over 35 cycles can be seen in FIG.23.

Active Electrolyte Adjustments Based on Open Circuit Voltage

To manage battery capacity on the string or site level, open circuitvoltage (OCV) values can be measured on the cell, stack, and batterylevel for each RFB in a string. OCV is the difference in electricalpotential between two terminals of a device when it is disconnected fromthe circuit. After measuring, a selected OCV value can be chosen as abaseline for the other batteries in the system. As a non-limitingexample, the selected OCV value may be the lowest OCV value in thestring. Therefore, in accordance with one embodiment of the presentdisclosure, the other RFBs in the string can then be adjusted tocorrespond to the selected OCV value. As another non-limiting example,the selected OCV value may have a predetermined OCV value compared toothers in the string.

In accordance with some embodiments of the present disclosure, adjustingthe OCV value for each battery includes transferring a volume ofcatholyte to the anolyte storage tank or a volume of anolyte to thecatholyte storage tank. In another embodiment of the present disclosure,adjusting the OCV value for each battery includes transferring a volumeof catholyte from another source outside the battery, such as fromanother battery, to the anolyte storage tank or a volume of anolyte fromanother source outside the battery, such as from another battery, to thecatholyte storage tank.

In one embodiment of the present disclosure, active capacity managementutilizes positive electrolyte pump pressure, managed by control valves,to transfer electrolyte from the anolyte pump discharge line to thecatholyte return line or from the catholyte pump discharge line to theanolyte return line. Such pump may be the same or different from a pumpused for actively transferring electrolyte from one to the other of thecatholyte and anolyte tanks, as described above. Active measures forcapacity management may be controlled by the BMS as dictated byoperating conditions. In other embodiments, active transfer can beaccomplished manually or semi automatically using external pumps orother common fluid transfer devices.

Another form of active capacity management is to automatically ormanually inject reactants into the electrolyte to cause a chemicalrebalancing. In one example, a measured amount of fructose is added tothe catholyte, which is reduced according to the following formula:

C₆H₁₂O₆+24VO₂ ⁺+24H⁺=24VO²⁺+6CO₂↑+18H₂O.

In other embodiments of the present disclosure, other reducing agentsmay be added to the catholyte, including but not limited to sugars,alcohols, organic acids, oils, hydrocarbons, and any combinationthereof. In yet other embodiments of the present disclosure, otheroxidizing agents may be added to the anolyte, including but not limitedto air, oxygen, hydrogen peroxide, ozone, and any combinations thereof.

Adjusting OCV may be controlled by the battery management system (BMS)during battery operation or may be performed during maintenance of theredox flow battery.

Example 9 Stack Performance Recovery

In a string of three, series-connected, kW-scale batteries with capacitymanagement adjustments, the energy density decline of about 7% is shownin FIG. 24 for over 200 cycles. As compared to the energy densitydecline in FIG. 22 of about 7% over only 35 cycles, matching operationmitigates performance degradation of a battery string.

Gas Generation During Operation

As discussed above, most RFBs have side reactions, such as hydrogengeneration. Hydrogen generation increases the average oxidation state ofthe electrolytes, which can result in a capacity decrease. In addition,hydrogen gas generation in a closed space can create safety concerns.Further, most RFB negative electrolyte solutions include strongreductants that can be oxidized by oxygen in the air. Such oxidationalso increases the average oxidation state of the electrolytes, whichcan result in a capacity decrease, as discussed below in EXAMPLE 10.

For chloride-containing redox flow battery systems, a small amount ofchlorine gas may be generated. Chlorine gas is a strong oxidant, andtherefore, can be rapidly absorbed by the negative electrolyte solutionsthrough surface contact if the chlorine gas is permitted to travel tothe headspace of the anolyte, as discussed below with reference to a gasmanagement system.

Example 10 Anolyte Instability when Exposed to Air

The anolyte in a VRB was exposed to air with a solution-air contactsurface ratio of 2.6 cm. As seen in FIG. 27, the anolyte state of chargedecreased rapidly from over 70% to 0% in less than 25 hours.

Gas Management System

A gas management system can be employed to manage the gasses generatedin a RFB. Although the gas management system described herein isdesigned for a vanadium redox flow battery, the same gas managementsystem concepts may be applied to other non-vanadium redox flowbatteries.

With reference to the simplified schematic in FIG. 25, the components ofthe gas management system 94 will now be described. As discussed above,catholyte and anolyte tanks 22 and 24 are in a substantially sealedsystem with liquid electrolyte in each tank, and each tank may include aheadspace above the respective anolyte and catholyte. In the illustratedembodiment, the headspaces above the anolyte and catholyte have free gasexchange with the respective anolyte and catholyte. In the illustratedembodiment, the gas management system 94 includes the gas headspaces 66and 68, a gas transfer device between the catholyte and anolyte tanks 22and 24, such as electrolyte transfer conduit 92 (which also allows forgas transfer), and a gas pressure management system 96 (shown as U-tube100, to be described in greater detail below). In one embodiment, asdiscussed above, the gas transfer device may be a conduit that allowsfor gas in the respective anolyte and catholyte headspaces to diffuseand exchange with each other. The rate of exchange is determined by thecross-section area, length of the conduit, and gas diffusion rate.

During operation, anolyte and catholyte tanks 22 and 24 are filled withelectrolyte up to a fill line allowing for a headspace in each tank 22and 24, and then sealed. The RFB system 20 is started in operation andthe gas compositions of the headspaces start to change as oxidationstarts to occur and hydrogen starts to be generated, as seen in FIG. 29.In one mode of operation, air is present in the respective headspaces ofthe anolyte and catholyte headspaces during electrolyte filling or othermaintenance operations when the tanks are sealed. In another embodiment,the headspaces are purged with nitrogen or another inert gas as part ofthe sealing process.

As discussed above, the tank system may include a tank electrolytetransfer conduit 92 located at or below an overflow level in either theanolyte or catholyte tank 22 or 24. The electrolyte transfer conduit 92may allow for the transfer of liquid electrolyte and gas exchange fromthe headspaces in the anolyte and catholyte tanks 22 and 24. If thetransfer of gas from the headspaces in the anolyte and catholyte tanks22 and 24 is provided in the electrolyte transfer conduit 92, then theelectrolyte transfer conduit 92 is also a part of the gas managementsystem for the RFB 20.

In another embodiment, the gas transfer device may be an independent gastransfer device different from the electrolyte transfer conduit 92. Forexample, the gas transfer device may be a conduit designed for gasexchange between the anolyte and catholyte headspaces 66 and 68, but notfor liquid electrolyte transfer. In another embodiment, the gas transferdevice may include one or more conduits which may be independent gastransfer devices or may be combined with an electrolyte transferconduit.

The gas transfer device (shown as electrolyte transfer conduit 92 in theillustrated embodiment of FIG. 25) provides a means to equalize thepressure between the anolyte and catholyte tanks, control the flow andexit location of gasses vented by the gas management system, and allowsfor diffusion of gas between the anolyte and catholyte tanks.

In one embodiment of the present disclosure, for example, a VRB,chlorine gas generated in the catholyte tank 24 by the followingequation diffuses through the gas transfer device 92 and moves to theheadspace in the anolyte tank 22.

Cl₂+2V²⁺=2V³⁺+2Cl⁻

When in the anolyte headspace over the anolyte surface, the chlorine gasis absorbed by the anolyte as it oxidizes to Cl₂O₂. The chlorine gasoxidizes quickly, before it has a chance to vent from the gas managementsystem 94 through the gas pressure management system 96, describedbelow.

Example 11 Chlorine Gas Absorption by Anolyte

As seen in FIG. 26, in an anolyte at 35 degrees Celsius having a gasvolume to gas-liquid surface ratio of 40 cm, chlorine concentration inthe gas phase at 1400 ppm is absorbed to 0 ppm in less than 80 minutes.

Gas Pressure Control

In addition to the gas transfer device, the gas management system 94 mayalso include one or more gas pressure management systems 96 to maintaina barrier between ambient air and the gas management system 94, controlgas pressure in the headspaces 66 and 68 of the gas management system94, and allow any necessary bi-directional pressure equalization betweenambient air and the gas management system 94. In that regard, the gaspressure management device 96 may allow for the release of excesshydrogen gas generated by the anolyte in the anolyte tank 22. The gaspressure management device 96 may also release carbon dioxide andnitrogen, and any other gases that may build up in the gas managementsystem 94. However, as discussed above, any chlorine gas generated by asystem (such as a vanadium redox flow battery containing chloride) tendsto be absorbed by the anolyte if the chlorine gas is allowed to migratefrom the headspace in the catholyte tank 24 to the headspace in theanolyte tank 22 through gas transfer device 92.

Referring to the illustrated embodiment of FIG. 13, the piping interface144 of the pump tub assembly 120 may also include a third connector 170that connects the head space 66 of the anolyte tank 22 and the headspace 68 of the catholyte tank 24 through the gas transfer device 92(see also FIG. 14A).

Referring to FIG. 25, in accordance with one embodiment of the presentdisclosure, the gas pressure control device is a U-shaped tube (U-tube)100 in fluid communication with the headspace 66 of the anolyte tank 22.Although shown in fluid communication with the headspace 66 of theanolyte tank 22, the U-tube 100 could also be suitable configured to bein fluid communication with the headspace 68 of the catholyte tank 24.

As illustrated in FIGS. 2 and 25, a connector point 172 provides anaccess position for the gas pressure management system 96 to the headspace 68 in the anolyte tank 22. However, other suitable connectorpoints are within the scope of the present disclosure. In theillustrated embodiment, the U-tube 100 has a U-shaped body 102 and afirst open end 104 in fluid communication with the headspace of the gasmanagement system 94 and a second open end 106 in fluid communicationwith an external atmosphere. The body 102 contains an amount of liquid108 that remains in the plumbing trap created by the U-shaped body 102between the first and second ends.

In the illustrated embodiment, the U-tube body 102 is a conduit whichmay have a constant cross-sectional area along the length of the U-tubefrom the first end 104 to the second end 106. In another embodiment, theU-tube body 102 may have a different cross-sectional area at the firstend, as compared to the second end (see FIG. 26).

The U-tube body may be designed to include baffles or enlarged sectionsto prevent the loss of liquid as a result of bubbling or a suddendischarge of gas.

As non-limiting examples, the U-tube may be filled with a liquidselected from the group consisting of water, an alkaline aqueoussolution, propylene glycol, ethylene glycol, an aqueous solution ofinorganic compound, an aqueous solution of organic compound, a waterinsoluble organic liquid, and combinations thereof, through whichcertain gases in the headspaces of the RFB will diffuse. A suitableliquid may be selected depending on the system, operating pressures, andtypes of gasses being emitted from the gas management system 94. Othersuitable liquids may be selected to provide certain operatingcharacteristics, for example, a desired temperature range or an abilityto scrub or eliminate undesired vent gases (such as chlorine) fromatmospheric discharge. In some non-limiting examples, the U-tube 100 mayinclude a combination of liquids, for example, an alkaline solution withan oil layer on top.

The U-tube 100 of the present disclosure allows for bi-directional gasexchange between the gas management system and the atmosphere. In theillustrated embodiment, the U-tube 100 is in fluid communication withthe anolyte headspace in the anolyte tank 22 and the atmosphere. In onenon-limiting example shown in FIGS. 26A and 26B, the U-tube 100 mayinclude, for example, 15 inches of water. When the pressure inside theanolyte headspace exceeds 15 inches of water, gases such as hydrogen maystart to bubble out of the tube into the atmosphere.

The U-tube may be configured to allow entry of an external gas into thegas management system when an exterior battery pressure exceeds aninterior battery pressure, for example, greater than or equal to 15inches water. In the same example, the U-tube will prevent the entry ofan external gas into the anolyte storage tank when the exterior batterypressure exceeds the interior battery pressure by less than 15 incheswater. In addition, the tank head space may have some flexibility toallow for expansion.

As seen in FIGS. 26A and 26B, the U-tube 100 may have a uniformcross-section at the first and second ends. In another embodiment of thepresent disclosure shown in FIGS. 26C and 26D, a U-tube 200 may have adifferent cross-sectional area at the first end, as compared to thesecond end. The effect of a change in cross-sectional area is that thepressure set points for gas entering and leaving the gas managementsystem may be different. For example, the first and second endcross-sectional areas may be sized so that the pressure requirement forgas exiting the gas management system is 15 inches of water, but thepressure requirement for gas entering the gas management system from theatmosphere is only 6 inches of water.

In one embodiment of the present disclosure, the interior batterypressure in the anolyte headspace is between −10 kPa and 10 kPa, −5 kPato +5 kPa, and −3 kPa to +3 kPa.

As a non-limiting example, a U-tube 100 may have a length of 24 inchesand a uniform diameter at the first and second ends of 2 inches. Asanother non-limiting example, a U-tube may have a length of 24 inchesand a non-uniform diameter at the first and second ends of 1.5 and 2inches. As described above, such variations may independently change thepressure regulation and the resulting rate of transfer of gases into orout of the gas management system.

In accordance with other embodiments of the present disclosure, the gaspressure management device may include more than one U-tube device, oneor more pressure regulating valves, one or more check vales, or acombination of these or other pressure management devices.

As discussed above, hydrogen generation can be a concern in RFBs. Inthat regard, hydrogen in combination with other gases may reach aflammability limit and pose a risk of ignition. The closed gasmanagement system mitigates this risk by keeping constituent gases intank head spaces below flammability limits as described below inEXAMPLES 12 and 13.

Example 12 Gas Phase Composition Change During Battery Operation

As seen in FIG. 29, hydrogen, oxygen, and nitrogen gas phase compositionchanges during battery operation. In that regard, hydrogen is generatedby side reactions, from 0% to about 60% after 60 hours of operation.Oxygen decreased from about 20% to less than 5% after 60 hours ofoperation. The oxygen was consumed by a vanadium oxidation reaction.Nitrogen decreased from about 80% to about 35%.

Example 13 Limits of Flammability of Hydrogen

As seen in FIG. 30, H. F. Coward and G. W. Jones, Limits of Flammabilityof Gases and Vapors, Bureau of Mines Bulletin 503 (1952), when theoxygen level in air and carbon dioxide or nitrogen is less than 5%, thegas mixture is not flammable. Because the gas management system is aclosed system, no additional oxygen becomes available.

Active Recovery of Average Oxidation State

As discussed above, in addition to electrolyte transfer between theanolyte and catholyte tanks, high electrolyte average oxidation statecan be recovered by adding reductive reagents to the positiveelectrolytes. Suitable reagents may include hydrocarbons, such asfructose. These reductive reagents can be oxidized by the catholyte,releasing carbon dioxide. Such reductive reagents may be addedperiodically, for example, during scheduled maintenance or automaticallyby the BMS system during battery operation.

Carbon dioxide generated during this process purges chlorine gas out ofthe catholyte tank through the gas transfer device to the anolyte tank.As described above, the chlorine gas can then be absorbed in theanolyte. In addition, the generation of carbon dioxide can also purgehydrogen out of the battery system through the gas pressure managementdevice. With reference to EXAMPLE 13 above, the addition of carbondioxide to the gas management system helps maintain the non-flammablecharacteristics of the gas management system.

Example 14 Fructose Addition

As seen in FIG. 31, energy density and average oxidation state wererecovered from about 19.25 Wh/L to over 20 Whr/L after the addition offructose to the catholyte.

Fructose added to the catholyte is reduced according to the followingformula, consuming hydrogen and generating carbon dioxide and water:

C₆H₁₂O₆+24VO₂ ⁺+24H⁺=24VO²⁺+6CO₂↑+18H₂O.

Therefore, as described above, the substantially closed gas head spacesof the illustrated embodiment can be managed to minimize energy capacityloss over time, and to maintain a non-flammable atmosphere to maximizeoperating safety.

Anti-Siphoning Feature

In addition to providing pressure management and other featurespreviously described, the gas management system 94 can also beconfigured to provide an anti-siphoning capability to prevent siphoningof electrolyte from one battery container compartment to another in theevent of a leak in the electrolyte circulation system 40. For example,an anti-siphoning arrangement may be used to prevent electrolyte in theelectrolyte tanks 22 and 24 in the second container compartment 62 shownin FIG. 3B from siphoning into the first container compartment 60 thathouses the cell stacks e.g., 30, 32, and 34, and other auxiliary andelectrical equipment in the event of a pipe rupture in the smaller frontcontainer compartment.

In one embodiment, illustrated in FIG. 7, and described in detail below,a siphon break 180 may be provided without any active measures orvalves. T-shaped tubing 186 connects the catholyte pump discharge 182 tothe catholyte pump return 184, and this connecting tube 186 is alsoconnected to the head space 188 of the catholyte tank 24. Whenelectrolyte is being circulated, a certain amount of electrolytecontinuously returns directly to the catholyte tank 24 through thetubing 186. When pumping stops, the tubing 186 connection to the headspace 188 provides a siphon break.

In another embodiment, illustrated in FIG. 34, a siphon break includesan anti-siphon conduit connecting a high point in the electrolytecirculation system with the head space of one of the first and secondcontainers or electrolyte tanks 22 and 24. The high point should behigher than the liquid level in the electrolyte tanks 22 and 24, butneed not be the highest point in the system.

The siphon break includes a first anti-siphon conduit 196 connecting thefirst container 24 discharge conduit 182 with the first container headspace 190 and a second anti-siphon conduit 198 connecting the firstcontainer return conduit 184 with the first container head space 190.Likewise, the same arrangement can be installed on the anolyte tank 22(not shown in FIG. 34). In the illustrated embodiment, the siphon breakdoes not include a valve.

The tubing 196 can be sized to a length and diameter to minimize pumpinglosses while allowing a siphon break to occur in an acceptable amount oftime. In one non-limiting example, the tubing 196 may have an insidediameter of 4 mm and a length of 3.8 meters to provide a siphon breakwithin 1 minute while minimizing pumping losses.

The fluidic connection may be tubing, piping, or some other suitableconduit that is sized in diameter and length to minimize pumping losseswhile proving passive anti-siphon action when pumping stops. Althoughactive systems are within the scope of the present disclosure,advantages of a passive arrangement include the following: no activecontrol is required; the tubing 186 are constantly flushed to maintainoperability; the system is passive, and reliability is increased.

Alternate anti-siphoning embodiments that may be used to preventsiphoning of electrolyte from one container compartment to anotherinclude a non-limiting arrangement of one or more passive or activedevices such as check valves, float valves, degassing valves, oractivated valves.

Battery Energy Density

Evolving demands and applications for large-scale energy storage systemsdrive the requirement for energy dense packaging that provides siteflexibility and ease of installation. Many RFB systems have relativelylow system level energy density, due in part to the combination of theirmethods of system packaging, for example the use of traditional externaltanks, or multiple containers that house the tanks separately from thebalance of plant (BOP). Other limitations of traditional system energydensity may be due to the inherent chemistry of the electrolyte, limitedspace availability for subsystems that manage shunt current losses,gasses, electrolyte utilization, or a combination of factors.

In accordance with aspects of the present disclosure, the tanks, thecontainer, and the remaining balance of plant system, such as thosedescribed above, can be configured as a self-contained, substantiallyclosed VRB unit that provides maximum energy storage capacity per unitsize of the container, while maintaining safe and reliable operatingcriteria. As such, RFB module 20 shown in FIGS. 1 and 2 constructed inaccordance with embodiments of the present disclosure can be configuredto have an energy density of 10 watt hours per liter of electrolyte(Wh/L) or greater for an RFB battery that has an energy capacity of atleast 2 kW-hours.

The RFB module 20 in embodiments of the present disclosure also may bedesigned to operate continuously while maintaining designed energydensity for a minimum of 50 or a minimum of 100 continuous fullcharge/discharge cycles or the equivalent operating hours withoutinterruption by service or user input.

General Arrangement

As discussed above the RFB module 20 described herein, as can be seen inFIGS. 1 and 2, is designed to be contained in a housing 50 havingspecific dimensions, for example as an ISO shipping container having alength A, width B, and height C. Space usage for the various componentsin the system can be optimized to maximize the amount of electrolytethat can be filled into the housing 50. As will be described in moredetail below, configuration of the battery, battery sub-systems, orcomponents themselves as well as the synergistic combinations of theseelements allow the RFB 20 to achieve the specified energy density, bothinitially and continuously over a period of time.

Space Utilization Features

As described above, electrolyte tanks can be manufactured to fit in theavailable space provided in a containerized and space-optimized RFBsystem. In that regard, the side-by-side design of the anolyte andcatholyte tanks 22 and 24 allows for maximization of the totalelectrolyte in the RFB 20, extending from bulkhead to rear wall.

The housing 50 is designed as structural support to facilitate the useof previously described flexible electrolyte tanks for space efficiency.In that regard, according to the present embodiment, the tanks 22 and 24are designed to fit closely within the housing 50, further reducingrequired tank wall thickness and inherent tank structural requirements,and maximizing tank volume for electrolyte containment in the RFB 20.Further, the housing is fully welded to provide compact secondarycontainment for the electrolyte in the event of a leak, further reducingtank thickness and maximizing tank volume.

In addition to the housing 50 design, other optional components in theRFB system are designed and arranged for enhanced use of space. Suchcomponents may be used individually in specific modules or together inconcert. For example, the pump tub assembly conserves BOP space in thefront of the battery container, while maximizing electrolyte tankheight, fill level, and volume available for electrolyte. In addition tospace utilization, the pump tub assembly also helps to minimize leakhazards in the battery module. In addition, as part of the electrolytecirculation system previously described, the looped fluid conduits 88(see FIGS. 1 and 2 provide for a compact shunt current mitigation systemthat maximizes fluid travel path length (component of current flowresistance), minimizes pumping losses, and improves battery overallefficiency in a small amount of space. Once again, this allows for moreavailable tank space to contain electrolyte.

To further optimize space efficiency, the designed anolyte and catholytetank volume ratio, such as a non-uniform tank volume ratio, can helpmaximum energy derived from a total electrolyte amount in both theanolyte and the catholyte.

Operational Features

In addition to space utilization features, one or more operationalpassive or active management features can be employed to improve theoperational efficiency of the RFB module and to also extend thecontinuous operational period of the RFB module without shutdown.

As noted above, in addition to maximizing the amount of electrolytecontained in the system to maximize energy density, the RFB system isalso designed to maintain such energy density over a certain number ofcycles, for example, 100 full charge/discharge cycles. To help maintainsystem capacity, one or more adjustments can be made to the electrolyteduring operation of the battery. For example, as the catholyte andanolyte volumes deviate from a predetermined volume, the system can bedesigned for a constant or periodic transfer of electrolyte from thecatholyte to the anolyte (or anolyte to catholyte) to maintainpredetermined tank electrolyte volumes, whether by active or passiveelectrolyte transfer methods. Moreover, individual batteries canautomatically be periodically adjusted to conform to a selected OCVvalue in a string to improve long-term performance.

In addition, an optional gas management system can be employed to removeor minimize reactions that decrease performance over time and mitigatethe effects of evolved gases from the electrolyte. Such gases, if leftunchecked, could be harmful to the system, create a safety hazard, orrequire environmental emissions monitoring, particularly chlorine andexcess hydrogen gas that may be generated in a RFB.

Electrolyte Composition

In addition to space management for maximizing the amount of electrolytecontained in the system to maximize energy density, the electrolyteitself may be formulated to enhance the energy storage capacity of theRFB. In accordance with embodiments of the present disclosure, in avanadium redox flow battery, vanadium concentration is selected from thegroup consisting of higher than 1.5M, higher than 1.8M, and higher than2.0M.

While embodiments have been illustrated and described, it will beappreciated that various changes can be made therein without departingfrom the spirit and scope of the disclosure.

The embodiments of the disclosure in which an exclusive property or privilege is claimed are defined as follows:
 1. A redox flow battery, comprising: an anolyte storage tank having a height configured for containing a quantity of an anolyte; a catholyte storage tank having a height configured for containing a quantity of a catholyte; an electrochemical cell configured for fluid communication with the anolyte and catholyte storage tanks; and a tub defining a cavity formed in at least one of the anolyte and catholyte storage tanks to provide a sealed fluid connection point below the height of the at least one storage tank.
 2. The redox flow battery of claim 1, wherein the tub is located such that a lower portion of the cavity is located below the liquid level in the tank and an upper portion of the cavity is located at or above the liquid level in the tank.
 3. The redox flow battery of claim 1, wherein the tub is a discreet tub attached to the at least one storage tank.
 4. The redox flow battery of claim 1, wherein the tub is a tub assembly including a plurality of components that are sealably attached to each other and to the at least one storage tank.
 5. The redox flow battery of claim 1, wherein the cavity opening is located on the top wall of the at least one storage tank.
 6. The redox flow battery of claim 1, wherein the cavity opening is located on the side wall of the at least one storage tank.
 7. The redox flow battery of claim 1, wherein a fluid connection point includes at least one of a pipe, pipe fitting, tube, tube fitting, pump, and filter, configured to transfer fluid between the storage tank and another device or system that is external to the storage tank envelope.
 8. The redox flow battery of claim 1, wherein a fluid connection point includes at least one of a pipe, pipe fitting, tube, tube fitting, pump, and filter configured to transfer gas between the storage tank and another device or system that is external to the storage tank envelope.
 9. The redox flow battery of claim 1, wherein the cavity contains a leak sensor configured to provide notification if liquid enters the cavity. 